Ceramic paste compositions for 3D printing

Abstract

The present invention relates to a ceramic paste composition comprising a matrix and water, wherein the matrix comprises, based on the total weight of the matrix: about 98 wt % to about 100 wt % of minerals of which at least 30 wt % are phyllosilicates and less than about 2 wt % organic additive; and wherein water is present from about 18 wt % to about 28 wt % based on the total weight of the ceramic paste composition. The present invention also relates to a method of forming a 3D structure using the ceramic paste composition of the invention.

The invention claimed is: 
     
         1 . A 3D printable ceramic paste composition comprising a matrix and water,
 wherein the matrix comprises, based on the total dry weight of the matrix:
 about 98 wt % to about 100 wt % of at least two minerals wherein at least 30 wt % of the at least two minerals are phyllosilicates; 
 less than about 2 wt % of an organic additive; and 
 the at least two minerals comprise kaolinite and at least one additional mineral; 
   and wherein water is present from about 20 wt % to about 28 wt % based on the total weight of the ceramic paste composition.   
     
     
         2 . The 3D printable ceramic paste composition of  claim 1 , wherein the at least one additional mineral is selected from illite, halloysite, montmorillonite, quartz, mica, orthoclase, albite, hematite, goethite, lime, dolomite, anatase, rutile, andalusite, anorthite, cordierite, smectite, muscovite, pyrophyllite, talc, diaoyudaoite, zircon, wollastonite, spodumene, nepheline syenite, magnesite, cristobalite, corundum, kyanite, sillimanite, borax, and magnesite. 
     
     
         3 . The 3D printable ceramic paste composition of  claim 1 , wherein the phyllosilicates are selected from halloysite, illite, smectite, talc, montmorillonite, muscovite, pyrophyllite, and combinations thereof. 
     
     
         4 . The 3D printable ceramic paste composition of  claim 1 , wherein the mean particle size distribution d 50  of the at least two minerals in the matrix is less than about 100 μm. 
     
     
         5 . The 3D printable ceramic paste composition of  claim 1 , wherein the organic additive is selected from methyl-cellulose, hydroxypropyl methyl-cellulose, hydroxyethyl methyl-cellulose, ethyl hydroxyethyl-cellulose, hydroxyethyl-cellulose, poly(ethylene oxide) polymer, carboxy-methylcellulose, polyethylenimine, poly(vinyl butyral), poly(ethylene glycol), poly(vinyl alcohol), poly(methacrylic acid), poly(acrylic acid), pectin citrus,  psyllium  husk powder, and combinations thereof. 
     
     
         6 . The 3D printable ceramic paste composition of  claim 1 , wherein the composition comprises an aggregate. 
     
     
         7 . The 3D printable ceramic paste composition of  claim 6 , wherein the aggregate is selected from kaolin grog, clay grog, mullite, andalusite, sillimanite, kyanite, fused corundum, ground ceramic waste, and combinations thereof. 
     
     
         8 . The 3D printable ceramic paste composition of  claim 6 , wherein the particle size distribution of the aggregate is from about 100 μm to about 500 μm. 
     
     
         9 . The 3D printable ceramic paste composition of  claim 8 , wherein the aggregate is present in an amount up to about 50 wt % based on the total weight of the matrix. 
     
     
         10 . The 3D printable ceramic paste composition of  claim 1 , wherein the storage modulus G′ of the 3D printable ceramic paste composition is between 1.0 E+6 Pa and 4.0 E+6 Pa. 
     
     
         11 . The 3D printable ceramic paste composition of  claim 1 , wherein loss modulus G″ of the 3D printable ceramic paste composition is between 1.5 E+5 Pa and 10.0 E+5 Pa. 
     
     
         12 . A method of forming a 3D ceramic structure from the 3D printable ceramic paste composition of  claim 1  using additive manufacturing. 
     
     
         13 . The method according to  claim 12 , wherein the additive manufacturing is a microextrusion method. 
     
     
         14 . The method of  claim 13 , wherein the microextrusion method is paste deposition modelling. 
     
     
         15 . The 3D printable ceramic paste composition of  claim 7 , wherein the particle size distribution of the aggregate is from about 100 μm to about 500 μm. 
     
     
         16 . The 3D printable ceramic paste composition of  claim 15 , wherein the aggregate is present in an amount up to about 50 wt % based on the total weight of the matrix. 
     
     
         17 . The 3D printable ceramic paste composition of  claim 2 , wherein:
 the phyllosilicates are selected from halloysite, illite, smectite, talc, montmorillonite, muscovite, pyrophyllite, and combinations thereof; and   the organic additive is selected from methyl-cellulose, hydroxypropyl methyl-cellulose, hydroxyethyl methyl-cellulose, ethyl hydroxyethyl-cellulose, hydroxyethyl-cellulose, poly(ethylene oxide) polymer, carboxy-methylcellulose, polyethylenimine, poly(vinyl butyral), poly(ethylene glycol), poly(vinyl alcohol), poly(methacrylic acid), poly(acrylic acid), pectin citrus,  psyllium  husk powder, and combinations thereof.   
     
     
         18 . The 3D printable ceramic paste composition of  claim 17 , wherein the mean particle size distribution d 50  of the at least two minerals in the matrix is less than about 100 μm. 
     
     
         19 . The 3D printable ceramic paste composition of  claim 18 , wherein 30 wt % to 55 wt % of the at least two minerals are phyllosilicates.